Polyethylene copolymers and products and methods thereof

ABSTRACT

A polymer composition may include a polymer produced from ethylene, and one or more vinyl carbonyl monomers having the general structure (I): 
     
       
         
         
             
             
         
       
     
     where R 1 , R 2  and R 3  are independently selected from a group consisting of hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substituted cycloalkoxy, substituted aryl, and substituted heterocycles; and Y and Z are independently selected from a group consisting of O, (CR 5a R 5b ), (CHR 6a )—R 6b , phenylene, CH—OR 7 , and NR 8 , wherein R 5a , R 5b , R 6a , R 6b , and R 8  are independently selected from a group consisting of hydrogen, halogen, CH 2 , and alkyl, and wherein R 7  is independently selected from a group consisting of hydrogen; halogen; hydroxyl; alkyl; linear ether; cyclic ether; Si(R 9 ) 3 , wherein R 9  is independently selected from a group consisting of hydrogen, halogen, and alkyl; and (C═O)—R 10 , wherein R 10  is an alkyl; and R 4  is independently selected from a group consisting of halogen, hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substituted cycloalkoxy, substituted aryl, and substituted heterocycles, where the polymer composition has a number average molecular weight (M n ) ranging from 5 kDa to 10000 kDa obtained by GPC.

BACKGROUND

The manufacture of polyolefin materials such as polyethylene (PE) andpolypropylene (PP) are the highest production volume of a syntheticpolymer ever invented. The success of these materials were greatlyachieved due to its low production cost, energy efficiency, lowgreenhouse gas emission, versatility to produce a wide range of polymerswith different properties, and high polymer processability. The widerange of articles produced with polyolefin materials includes films,molded products, foams, pipes, textiles, and the like. These productsalso have the attractiveness to be recycled by pyrolysis to gas and oilor by incineration to energy. The physical and chemical properties ofpolyolefin compositions may exhibit varied responses depending on anumber of factors such as molecular weight, distribution of molecularweights, content, nature and distribution of comonomer (or comonomers),the presence of short and/or long chain-branches and its distribution,thermal and shear history, and the like, which define theirapplicability in certain applications. To increase their utilization,polyolefins may be formulated as random and block copolymers with anumber of possible comonomers, and as mixtures with a number ofpotential additives.

SUMMARY

This summary is provided to introduce a selection of concepts that arefurther described below in the detailed description. This summary is notintended to identify key or essential features of the claimed subjectmatter, nor is it intended to be used as an aid in limiting the scope ofthe claimed subject matter.

In one aspect, embodiments disclosed herein relate to a polymercomposition, that includes a polymer produced from ethylene, and one ormore vinyl carbonyl monomers having the general structure (I):

where R¹, R² and R³ are independently selected from a group consistingof hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,substituted alkoxy, alkenyl, substituted alkenyl, alkynyl, substitutedalkynyl, aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substitutedcycloalkyl, substituted cycloalkoxy, substituted aryl, and substitutedheterocycles; and Y and Z are independently selected from a groupconsisting of O, (CR^(5a)R^(5b)), (CHR^(6a))—R^(6b), phenylene, CH—OR⁷,and NR⁸, wherein R^(5a), R^(5b), R^(6a), R^(6b), and R⁸ areindependently selected from a group consisting of hydrogen, halogen,CH₂, and alkyl, and wherein R⁷ is independently selected from a groupconsisting of hydrogen; halogen; hydroxyl; alkyl; linear ether; cyclicether; Si(R⁹)₃, wherein R⁹ is independently selected from a groupconsisting of hydrogen, halogen, and alkyl; and (C═O)—R¹⁰, wherein R¹⁰is an alkyl; and R⁴ is independently selected from a group consisting ofhalogen, hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy,alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl,(heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substitutedcycloalkoxy, substituted aryl, and substituted heterocycles, and wherethe polymer composition has a number average molecular weight (M_(n))ranging from 5 kDa to 10000 kDa obtained by gel permeationchromatography (GPC).

In one aspect, embodiments disclosed herein relate to a polymercomposition, that includes a polymer produced from ethylene, and one ormore vinyl carbonyl monomers having the general structure (I):

where R¹, R² and R³ are independently selected from a group consistingof hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,substituted alkoxy, alkenyl, substituted alkenyl, alkynyl, substitutedalkynyl, aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substitutedcycloalkyl, substituted cycloalkoxy, substituted aryl, and substitutedheterocycles; and Y and Z are independently selected from a groupconsisting of O, (CR^(5a)R^(5b)), (CHR^(6a))—R^(6b), phenylene, CH—OR⁷,and NR⁸, wherein R^(5a), R^(5b), R^(6a), and R⁸ are independentlyselected from a group consisting of hydrogen, halogen, CH₂, and alkyl,and wherein R⁷ is independently selected from a group consisting ofhydrogen; halogen; hydroxyl; alkyl; linear ether; cyclic ether; Si(R⁹)₃,wherein R⁹ is independently selected from a group consisting ofhydrogen, halogen, and alkyl; and (C═O)—R¹⁰, wherein R¹⁰ is an alkyl;and R⁴ is independently selected from a group consisting of halogen,hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy, alkenyl,substituted alkenyl, alkynyl, substituted alkynyl, aralkyl,(heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substitutedcycloalkoxy, substituted aryl, and substituted heterocycles, and whereinwhen Y is O, the combined carbon count of Z and R⁴ is less than 8 ormore than 9.

In yet another aspect, embodiments disclosed herein relate to a polymercomposition, that includes a polymer produced from ethylene, and one ormore vinyl carbonyl monomers having the general structure (II):

wherein R¹¹, R¹², and R¹³ have a combined carbon number in the range ofC3 to C20 and the polymer composition has a number average molecularweight (M_(n)) ranging from 5 kDa to 10000 kDa obtained by GPC.

In yet another aspect, embodiment disclosed herein relate to a polymercomposition, that includes: a polymer produced from ethylene, and one ormore vinyl carbonyl monomers having the general structure (IV):

wherein R¹⁴ and R¹⁵ are independently selected from the group consistingof hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,substituted alkoxy, alkenyl, substituted alkenyl, alkynyl, substitutedalkynyl, aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substitutedcycloalkyl, substituted cycloalkoxy, substituted aryl, substitutedheterocycles, and Si(R⁹)₃, wherein R⁹ is selected from a groupconsisting of hydrogen, halogen, and alkyl; linear ether; cyclic ether.

In yet another aspect, embodiments disclosed herein relate to an articleprepared from a polymer composition having the above-described features.

In yet another aspect, embodiments disclosed herein relate to a methodof preparing a polymer composition that includes adding to a reactorethylene and one or more vinyl carbonyl monomers having the generalstructural formulae (I)-(IV) discussed above.

Other aspects and advantages of the claimed subject matter will beapparent from the following description and the appended claims.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows ¹³C NMR spectra for a number of samples in accordance withembodiments of the present disclosure.

FIG. 2 shows ¹H NMR spectra for a number of samples in accordance withembodiments of the present disclosure.

FIG. 3 shows ¹³C NMR spectra for a number of samples in accordance withembodiments of the present disclosure.

FIG. 4 shows ¹H NMR spectra for a number of samples in accordance withembodiments of the present disclosure.

FIG. 5 is a graphical depiction of viscometer gel permeationchromatography (GPC) chromatograph obtained for a number of samples inaccordance with embodiments of the present disclosure.

FIGS. 6A-6C are graphical depictions of a two-dimensional liquidchromatography (2D-LC) chromatographs for a number of samples inaccordance with embodiments of the present disclosure.

FIGS. 7A-7C is a graphical depiction of a differential scanningcalorimeter (DSC) spectra for a number of samples in accordance withembodiments of the present disclosure.

FIGS. 8A-8B are graphical depictions of a dynamic mechanical analysis(DMA) results for a number of samples in accordance with embodiments ofthe present disclosure.

FIGS. 9A-9B are graphical depictions of a thermal gravimetric analysis(TGA) thermogram for a number of samples in accordance with embodimentsof the present disclosure.

FIGS. 10A-10B are graphical depictions of a successive self-nucleationand annealing (SSA) results for a number of samples in accordance withembodiments of the present disclosure.

DETAILED DESCRIPTION

In one aspect, embodiments disclosed herein relate to polymercompositions containing copolymers prepared from ethylene and one ormore vinyl carbonyl and/or diene monomers. In one or more embodiments,polymer compositions may be prepared from a reaction of ethylene and oneor more branched vinyl esters and/or diene monomers that modify variousproperties of the formed copolymer including crystallinity, hardness,melt temperature, glass transition temperature, among others.

Polymer compositions in accordance with the present disclosure mayinclude copolymers incorporating various ratios of ethylene and one ormore vinyl esters and/or diene monomers, including one or more branchedvinyl esters. In some embodiments, polymer compositions may be preparedby reacting ethylene and a branched vinyl ester in the presence ofadditional comonomers and one or more radical initiators to form acopolymer. In other embodiments, terpolymers may be prepared by reactingethylene with a first comonomer to form a polymer resin or prepolymer,which is then reacted with a second comonomer to prepare the finalpolymer composition, wherein the first and the second comonomer can beadded in the same reactor or in different reactors. In one or moreembodiments, copolymers may be prepared by reacting ethylene and one ormore comonomers at one or more polymerization reaction stages to obtainvarious repeat unit microstructures. In one or more embodiments, thepolymer compositions may include polymers generated from monomersderived from petroleum and/or renewable sources.

Vinyl Carbonyl Monomers

In one or more embodiments, vinyl carbonyl monomers may be described bythe general structure (I):

where R¹, R² and R³ are independently selected from a group consistingof hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,substituted alkoxy, alkenyl, substituted alkenyl, alkynyl, substitutedalkynyl, aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substitutedcycloalkyl, substituted cycloalkoxy, substituted aryl, and substitutedheterocycles; and Y and Z are independently selected from a groupconsisting of O, (CR^(5a)R^(5b)), (CHR^(6a))—R^(6b), phenylene, CH—OR⁷,and NR⁸, wherein R^(5a), R^(5b), R^(6a), R^(6b), and R⁸ areindependently selected from a group consisting of hydrogen, halogen,CH₂, and alkyl, and wherein R⁷ is independently selected from a groupconsisting of hydrogen; halogen; hydroxyl; alkyl; linear ether; cyclicether; Si(R⁹)₃, wherein R⁹ is independently selected from a groupconsisting of hydrogen, halogen, and alkyl; and (C═O)—R¹⁰, wherein R¹⁰is an alkyl; and R⁴ is independently selected from a group consisting ofhalogen, hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy,alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl,(heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substitutedcycloalkoxy, substituted aryl, and substituted heterocycles. In one ormore embodiments, the number of carbon atoms within Z and R⁴ may rangefrom a lower limit of 2, 3, or 4 and an upper limit of 12, 16, 20, or24, where any lower limit can be used in combination with any upperlimit. In one or more embodiments, the polymer compositions may includepolymers generated from monomers derived from petroleum and/or renewablesources. In some embodiments, polymer compositions may include two ormore vinyl carbonyl monomers, including mixtures of isomers.

In one or more embodiments, vinyl carbonyl monomers may include vinylesters prepared from vinyl alcohol and a carboxylic acid, such as vinylacetate, vinyl propanoate, vinyl butanoate, vinyl pentanoate, vinylhexanoate, vinyl 2-methyl butanoate, vinyl 3-ethylpentanoate, vinyl3-ethylhexanoate, and the like. In one or more embodiments, when Y is Oin formula (I) above, Z and R⁴ may be selected from the above species tohave a combined carbon count of less than 8 or more than 9 (inparticular, to avoid resulting in neodecanoate and/or neononoate groups)when the M_(n) is less than 5 kDa. In one or more embodiments, thepolymer compositions may include polymers generated from monomersderived from petroleum and/or renewable sources.

In one or more embodiments, vinyl carbonyl monomers may include branchedvinyl esters, which may include branched vinyl esters generated fromisomeric mixtures of branched alkyl acids. Branched vinyl esters inaccordance with the present disclosure may have the general chemicalformula (II):

where R¹¹, R¹², and R¹³ have a combined carbon number in the range of C3to C20. In some embodiments, R¹¹, R¹², and R¹³ may all be alkyl chainshaving varying degrees of branching in some embodiments, or a subset ofR¹¹, R¹², and R¹³ may be independently selected from a group consistingof hydrogen, alkyl, or aryl in some embodiments.

In one or more embodiments, the vinyl carbonyl monomers may includebranched vinyl esters having the general chemical formula (III):

wherein R¹⁶ and R¹⁷ have a combined carbon number of 6 or 7 and thepolymer composition has a number average molecular weight (Mn) rangingfrom 5 kDa to 1000 kDa obtained by GPC. In one or more embodiments, R¹⁶and R¹⁷ may have a combined carbon number of less than 6 or greater than7, and the polymer composition may have an M_(n) up to 2000 kDa or 10000kDa. That is, when the M_(n) is less than 5 kDa, R¹⁶ and R¹⁷ may have acombined carbon number of less than 6 or greater than 7, but if theM_(n) is greater than 5 kDa, R¹⁶ and R¹⁷ may include a combined carbonnumber of 6 or 7.

Examples of branched vinyl esters may include monomers having thechemical structures, including derivatives thereof:

In one or more embodiments, the polymer compositions may includepolymers generated from monomers derived from petroleum and/or renewablesources.

In one or more embodiments, branched vinyl esters may include monomersand comonomer mixtures containing vinyl esters of neononanoic acid,neodecanoic acid, and the like. In some embodiments, branched vinylesters may include Versatic™ acid series tertiary carboxylic acids,including Versatic™ acid EH, Versatic™ acid 9 and Versatic™ acid 10prepared by Koch synthesis, commercially available from Hexion™chemicals. In one or more embodiments, the polymer compositions mayinclude polymers generated from monomers derived from petroleum and/orrenewable sources.

In one or more embodiments, vinyl carbonyl monomers may have the generalchemical formula (IV):

where R¹⁴ and R¹⁵ are independently selected from the group consistingof hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,substituted alkoxy, alkenyl, substituted alkenyl, alkynyl, substitutedalkynyl, aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substitutedcycloalkyl, substituted cycloalkoxy, substituted aryl, substitutedheterocycles, and Si(R⁹)₃, wherein R⁹ is selected from a groupconsisting of hydrogen, halogen, and alkyl; linear ether; cyclic ether.In one or more embodiments vinyl carbonyl monomers may include alkylvinyl glycolates such as methyl vinyl glycolate, ethyl vinyl glycolate,and the like.

Examples of other vinyl carbonyl monomers according to formula (I) and(IV) also include monomers having the chemical strucures, includingderivatives thereof:

Diene Monomers

In one or more embodiments, the polymer compositions may optionallyinclude diene monomers with the ethylene and one or more vinyl carbonylmonomers discussed above. In some embodiments, diene monomers may havethe chemical structures as presented below, including derivativesthereof:

to modify various polymer properties.

Polymer compositions in accordance with the present disclosure mayinclude a percent by weight of ethylene measured by proton nuclearmagnetic resonance (¹H NMR) and Carbon 13 nuclear magnetic resonance(¹³C NMR) that ranges from a lower limit selected from one of 0.1 wt %,0.5 wt %, 1 wt %, and 5 wt %, to an upper limit selected from one of 90wt %, 95 wt %, 99.9 wt %, and 99.99 wt %, where any lower limit may bepaired with any upper limit.

In some embodiments, polymer compositions in accordance with the presentdisclosure may optionally include a percent by weight of vinyl acetatemeasured by ¹H NMR and ¹³C NMR that ranges from a lower limit selectedfrom one of 0.01 wt %, 0.1 wt %, 0.5 wt %, 1 wt %, 5 wt %, 10 wt %, 20wt % and 30 wt % to an upper limit selected from 60 wt %, 70 wt %, 80 wt% and 90 wt % where any lower limit may be paired with any upper limit.

Polymer compositions in accordance with the present disclosure mayinclude a percent by weight of vinyl carbonyl monomer (other than vinylacetate) measured by ¹H NMR and ¹³C NMR that ranges from a lower limitselected from one of 0.01 wt %, 0.1 wt %, 0.5 wt %, 1 wt %, 5 wt %, 10wt %, 20 wt % and 30 wt % to an upper limit selected from 60 wt %, 70 wt%, 80 wt % and 90 wt % where any lower limit may be paired with anyupper limit.

Polymer compositions in accordance with the present disclosure mayoptionally include a percent by weight of diene monomer measured by ¹HNMR and ¹³C NMR that ranges from a lower limit selected from one of 0.01wt %, 0.1 wt %, 0.5 wt %, 1 wt %, 5 wt %, 10wt %, 15 wt % and 20 wt % toan upper limit selected from 30 wt %, 35 wt %, 40 wt % and 50 wt % whereany lower limit may be paired with any upper limit.

Polymer compositions in accordance with the present disclosure may havea number average molecular weight (M_(n)) in kilodaltons (kDa) measuredby gel permeation chromatography (GPC) of the polymer composition rangesfrom a lower limit selected from one of 1 kDa, 5 kDa, 10 kDa, 20 kDa,and 40 kDa to an upper limit selected from one of 100 kDa, 300 kDa, 500kDa, 1000 kDa, 2000 kDa, 5000 kDa, or 10000 kDa where any lower limitmay be paired with any upper limit.

Polymer compositions in accordance with the present disclosure may havea weight average molecular weight (M_(w)) in kilodaltons (kDa) measuredby GPC of the polymer composition ranges from a lower limit selectedfrom one of 1 kDa, 5 kDa, 10 kDa, 15 kDa and 20 kDa to an upper limitselected from one of 40 kDa, 50 kDa, 100 kDa, 200 kDa, 300 kDa, 500 kDa,1000 kDa, 5000 kDa, 10000 kDa and 20000 kDa where any lower limit may bepaired with any upper limit.

Polymer compositions in accordance with the present disclosure may havea molecular weight distribution (MWD, obtained from the ratio betweenM_(w) and M_(n)) measured by GPC that has a lower limit of any of 1, 2,5, or 10, and an upper limit of any of 20, 30, 40, 50, or 60, where anylower limit may be paired with any upper limit.

Initiators for Free-Radical Polymerization

Polymer compositions in accordance with the present disclosure mayinclude one or more initiators for radical polymerization capable ofgenerating free radicals that initiate chain polymerization ofcomonomers and prepolymers in a reactant mixture. In one or moreembodiments, radical initiators may include chemical species thatdegrade to release free radicals spontaneously or under stimulation bytemperature, pH, or other trigger.

In one or more embodiments, radical initiators may include peroxides andbifunctional peroxides such as benzoyl peroxide; dicumyl peroxide;di-tert-butyl peroxide; tert-butyl cumyl peroxide;t-butyl-peroxy-2-ethyl-hexanoate; tert-butyl peroxypivalate; tertiarybutyl peroxyneodecanoate; t-butyl-peroxy-benzoate;t-butyl-peroxy-2-ethyl-hexanoate; tert-butyl 3,5,5-trimethylhexanoateperoxide; tert-butyl peroxybenzoate; 2-ethylhexyl carbonate tert-butylperoxide; 2,5-dimethyl-2,5-di (tert-butylperoxide) hexane; 1,1-di(tert-butylperoxide)-3,3,5-trimethylcyclohexane;2,5-dimethyl-2,5-di(tert-butylperoxide) hexyne-3;3,3,5,7,7-pentamethyl-1,2,4-trioxepane; butyl 4,4-di(tert-butylperoxide) valerate; di (2,4-dichlorobenzoyl) peroxide;di(4-methylbenzoyl) peroxide; peroxide di(tert-butylperoxyisopropyl)benzene; and the like.

Radical initiators may also include benzoyl peroxide,2,5-di(cumylperoxy)-2,5-dimethyl hexane,2,5-di(cumylperoxy)-2,5-dimethylhexyne-3,4-methyl-4-(t-butylperoxy)-2-pentanol,4-methyl-4-(t-amylperoxy)-2-pentano1,4-methyl-4-(cumylperoxy)-2-pentanol,4-methyl-4-(t-butylperoxy)-2-pentanone,4-methyl-4-(t-amylperoxy)-2-pentanone,4-methyl-4-(cumylperoxy)-2-pentanone,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-amylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(t-amylperoxy)hexyne-3,2,5-dimethyl-2-t-butylperoxy-5-hydroperoxyhexane,2,5-dimethyl-2-cumylperoxy-5-hydroperoxy hexane,2,5-dimethyl-2-t-amylperoxy-5-hydroperoxyhexane, m/p-alpha,alpha-di[(t-butylperoxy)isopropyl]benzene,1,3,5-tris(t-butylperoxyisopropyl)benzene,1,3,5-tris(t-amylperoxyisopropyl)benzene,1,3,5-tris(cumylperoxyisopropyl)benzene,di[1,3-dimethyl-3-(t-butylperoxy)butyl]carbonate, di[1,3-dimethyl-3-(t-amylperoxy) butyl]carbonate,di[1,3-dimethyl-3-(cumylperoxy)butyl]carbonate, di-t-amyl peroxide,t-amyl cumyl peroxide, t-butyl-isopropenylcumyl peroxide,2,4,6-tri(butylperoxy)-s-triazine,1,3,5-tri[1-(t-butylperoxy)-1-methylethyl]benzene,1,3,5-tri-[(t-butylperoxy)-isopropyl]benzene,1,3-dimethyl-3-(t-butylperoxy)butanol,1,3-dimethyl-3-(t-amylperoxy)butanol,di(2-phenoxyethyl)peroxydicarbonate,di(4-t-butylcyclohexyl)peroxydicarbonate, dimyristyl peroxydicarbonate,dibenzyl peroxydicarbonate, di(isobomyl)peroxydicarbonate,3-cumylperoxy-1,3-dimethylbutyl methacrylate,3-t-butylperoxy-1,3-dimethylbutyl methacrylate,3-t-amylperoxy-1,3-dimethylbutylmethacrylate,tri(1,3-dimethyl-3-t-butylperoxy butyloxy)vinyl silane,1,3-dimethyl-3-(t-butylperoxy)butylN-[1-{3-(1-methylethenyl)-phenyl}-1-methylethyl]carbamate,1,3-dimethyl-3-(t-amylperoxy)butylN-[1-{3(1-methylethenyl)-phenyl}-1-methylethyl]carbamate,1,3-dimethyl-3-(cumylperoxy))butylN-[1-{3-(1-methylethenyl)-phenyl}-1-methylethyl]carbamate,1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-di(t-butylperoxy)cyclohexane, n-butyl 4,4-di(t-amylperoxy)valerate,ethyl 3,3-di(t-butylperoxy)butyrate, 2,2-di(t-amylperoxy)propane,3,6,6,9,9-pentamethyl-3-ethoxycabonylmethyl-1,2,4,5-tetraoxacyclononane,n-buty 1-4,4OO-t-amyl-O-hydrogen-monoperoxy-succinate, 3,6,9,triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (or methyl ethyl ketoneperoxide cyclic trimer), methyl ethyl ketone peroxide cyclic dimer,3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane,2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl perbenzoate,t-butylperoxy acetate, t-butylperoxy-2-ethyl hexanoate, t-amylperbenzoate, t-amyl peroxy acetate, t-butyl peroxy isobutyrate,3-hydroxy-1,1-dimethyl t-butyl peroxy-2-ethyl hexanoate,OO-t-amyl-O-hydrogen-monoperoxy succinate,OO-t-butyl-O-hydrogen-monoperoxy succinate, di-t-butyldiperoxyphthalate, t-butylperoxy (3,3,5-trimethylhexanoate),1,4-bis(t-butylperoxycarbo)cyclohexane,t-butylperoxy-3,5,5-trimethylhexanoate,t-butyl-peroxy-(cis-3-carboxy)propionate, allyl 3-methyl-3-t-butylperoxybutyrate, OO-t-butyl-O-isopropylmonoperoxy carbonate,OO-t-butyl-O-(2-ethyl hexyl) monoperoxy carbonate,1,1,1-tris[2-(t-butylperoxy-carbonyloxy)ethoxymethyl]propane,1,1,1-tris[2-(t-amylperoxy-carbonyloxy)ethoxymethyl]propane,1,1,1-tris[2-(cumylperoxy-cabonyloxy)ethoxymethyl]propane,OO-t-amyl-O-isopropylmonoperoxy carbonate, di(4-methylbenzoyl)peroxide,di(3-methylbenzoyl)peroxide, di(2-methylbenzoyl)peroxide, didecanoylperoxide, dilauroyl peroxide, 2,4-dibromo-benzoyl peroxide, succinicacid peroxide, dibenzoyl peroxide, di(2,4-dichloro-benzoyl)peroxide, andcombinations thereof.

In one or more embodiments, radical initiators may include azo-compoundssuch as azobisisobutyronitrile (AIBN), 2,2′-azobis(amidinopropyl)dihydrochloride, and the like, azo-peroxide initiators that containmixtures of peroxide with azodinitrile compounds such as2,2′-azobis(2-methyl-pentanenitrile),2,2′-azobis(2methyl-butanenitrile), 2,2′-azobis(2-ethyl-pentanenitrile),2-[(1-cyano-1-methylpropyl)azo]-2-methyl-pentanenitrile,2-[(1-cyano-1-ethylpropyl)azo]-2-methyl-butanenitrile,2-[(1-cyano-1-methylpropyl)azo]-2-ethyl, and the like.

In one or more embodiments, radical initiators may include Carbon-Carbon(“C═C”) free radical initiators such as 2,3-dimethyl-2,3-diphenylbutane,3,4-dimethyl-3,4-diphenylhexane, 3,4-diethyl-3,4-diphenylhexane,3,4-dibenzyl-3,4ditolylhexane,2,7-dimethyl-4,5-diethyl-4,5-diphenyloctane,3,4-dibenzyl-3,4-diphenylhexane, and the like.

In one or more embodiments, polymer compositions in accordance with thepresent disclosure may be formed from one or more radical initiatorspresent at a percent by weight of the total polymerization mixture (wt%) that ranges from a lower limit selected from one of 0.000001 wt %,0.0001 wt %, 0.01 wt %, 0.1 wt %, 0.15 wt %, 0.4 wt %, 0.6 wt %, 0.75 wt% and 1 wt %, to an upper limit selected from one of 0.5 wt %, 1.25 wt%, 2 wt %, 4 wt %, and 5 wt %, where any lower limit can be used withany upper limit. Further, it is envisioned that the concentration of theradical initiator may be more or less depending on the application ofthe final material.

Stabilizers

Polymer compositions in accordance with the present disclosure mayinclude one or more stabilizers capable of preventing polymerization inthe feed lines of monomers and comonomers but not hinderingpolymerization at the reactor.

In one or more embodiments, stabilizers may include nitroxyl derivativessuch as 2,2,6,6-tetramethyl-1-piperidinyloxy,2,2,6,6-tetramethyl-4-hydroxy-1-piperidinyloxy,4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy,2,2,6,6-tetramethyl-4-amino-piperidinyloxy, and the like.

In one or more embodiments, polymer compositions in accordance with thepresent disclosure be formed from one or more stabilizers present at apercent by weight of the total polymerization mixture (wt %) of one ormore stabilizers that ranges from a lower limit selected from one of0.000001 wt %, 0.0001 wt %, 0.01 wt %, 0.1 wt %, 0.15 wt %, 0.4 wt %,0.6 wt %, 0.75 wt % and 1 wt %, to an upper limit selected from one of0.5 wt %, 1.25 wt %, 2 wt %, 4 wt %, and 5 wt %, where any lower limitcan be used with any upper limit. Further, it is envisioned that theconcentration of the stabilizer may be more or less depending on theapplication of the final material.

Additives

Polymer compositions in accordance with the present disclosure mayinclude fillers and additives that modify various physical and chemicalproperties when added to the polymer composition during blending thatinclude one or more polymer additives such as kickers, processing aids,lubricants, antistatic agents, clarifying agents, nucleating agents,beta-nucleating agents, slipping agents, antioxidants, antacids, lightstabilizers such as HALS, IR absorbers, whitening agents, organic and/orinorganic dyes, anti-blocking agents, processing aids, flame-retardants,plasticizers, biocides, and adhesion-promoting agents.

Polymer compositions in accordance with the present disclosure mayinclude one or more inorganic fillers such as talc, glass fibers, marbledust, cement dust, clay, carbon black, feldspar, silica or glass, fumedsilica, silicates, calcium silicate, silicic acid powder, glassmicrospheres, mica, metal oxide particles and nanoparticles such asmagnesium oxide, antimony oxide, zinc oxide, inorganic salt particlesand nanoparticles such as barium sulfate, wollastonite, alumina,aluminum silicate, titanium oxides, calcium carbonate, polyhedraloligomeric silsesquioxane (POSS).

In one or more embodiments, polymer compositions in accordance with thepresent disclosure may contain a percent by weight of the totalcomposition (wt %) of one or more additives and/or fillers that rangesfrom a lower limit selected from one of 0.01wt %, 0.02 wt %, 0.05 wt %,1.0 wt %, 5.0 wt %, 10.0 wt %, 15.0 wt %, and 20.0 wt %, to an upperlimit selected from one of 25 wt %, 30 wt %, 40 wt %, 50 wt %, 60 wt %,and 70 wt %, where any lower limit can be used with any upper limit.

Polymer Composition Preparation Methods

In one or more embodiments, polymer compositions in accordance with thepresent disclosure may be prepared in reactor by polymerizing ethyleneand one or more vinyl carbonyl and/or diene monomers. Methods ofreacting the comonomers in the presence of a radical initiator mayinclude any suitable method in the art including solution phasepolymerization, pressurized radical polymerization, bulk polymerization,emulsion polymerization, and suspension polymerization. In someembodiments, the reactor may be a batch or continuous reactor atpressures below 500 bar, known as low pressure polymerization system. Inparticular embodiments, the reactor pressure may be above 40 bar, andthe reactor temperature may be above 50° C., and including theconditions known as high pressure polymerizations. In one or moreembodiments, the reaction is carried out in a low pressurepolymerization process wherein the ethylene and one or more vinylcarbonyl are polymerized in a liquid phase of an inert solvent and/orone or more liquid monomer(s). In one embodiment, polymerizationcomprises initiators for free-radical polymerization in an amount fromabout 0.0001 to about 0.01 milimoles calculated as the total amount ofone or more initiator for free-radical polymerization per liter of thevolume of the polymerization zone. The amount of ethylene in thepolymerization zone will depend mainly on the total pressure of thereactor in a range from about 20 bar to about 500 bar and temperature ina range from about 20° C. to about 200° C. In one or more embodiments,the pressure in the reactor may have a lower limit of any of 20, 30, 40,50, 75, or 100 bar, and an upper limit of any of 100, 150, 200, 250,300, 350, 400, 450 or 500 bar. The liquid phase of the polymerizationprocess in accordance with the present disclosure may include ethylene,one or more vinyl carbonyl monomer, initiator for free-radicalpolymerization, and optionally one or more inert solvent such astetrahydrofuran (THF), chloroform, dichloromethane (DCM), dimethylsulfoxide (DMSO), dimethyl carbonate (DMC), hexane, cyclohexane, ethylacetate (EtOAc) acetonitrile, toluene, xylene, ether, dioxane,dimethyl-formamide (DMF), benzene or acetone. Copolymers and terpolymersproduced under low-pressure conditions may exhibit number averagemolecular weights of 1 to 300 kDa, weight average molecular weights of 1to 1000 kDa and MWDs of 1 to 60.

In some embodiments, the comonomers and one or more free-radicalpolymerization initiators are polymerized in a continuous or batchprocess at temperatures above 70 ° C. and at pressures above 1000 bar,known as high pressure polymerization systems. For example, a pressureof greater than 1000, 1100, 1200, 1500, 1600, 1700, 1800, 1900, 2000,2100, 2200, 2300, 2400, 2500, 3000, 5000, or 10000 bar may be used.Copolymers and terpolymers produced under high-pressure conditions mayhave number average molecular weights (M_(n)) of 1 to 10000 kDa, weightaverage molecular weights (M_(w)) of 1 to 20000 kDa. Molecular weightdistribution (MWD) is obtained from the ratio between the weight averagemolecular weight (M_(w)) and the number average molecular weight (M_(n))obtained by GPC. Copolymers and terpolymers produced under high-pressureconditions may have MWDs of 1 to 60.

In some embodiments, the conversion during polymerization in lowpressure polymerization and high pressure polymerization systems, whichis defined as the weight or mass flow of the produced polymer divided bythe weight of mass flow of monomers and comonomers may have a lowerlimit of any of 0.01%, 0.1%, 1%, 2%, 5%, 7%, 10% and a upper limit ofany of 15%, 17%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%,99% or 100%.

Physical Properties

In one or more embodiments, polymer compositions may have a melt flowrate (MFR) according to ASTM D1238 at 190° C./2.16 kg in a range havinga lower limit selected from any of 0.01 g/10 min, 0.5 g/10 min, 1 g/10min, and 10 g/10 min, to an upper limit selected from any of 50 g/10min,350 g/10 min, 450 g/10 min, 550 g/10 min, 1000 g/10 min, and 2000 g/10min, where any lower limit may be paired with any upper limit.

In one or more embodiments, polymer compositions may have crystallinitymeasured according to ASTM D3418 by differential scanning calorimetry(DSC) or wide angle X-ray diffraction (WAXD) in a range having a lowerlimit selected from any 0.1%, 1%, 10%, and 20%, to an upper limitselected from any of 60%, 70%, and 80%, where any lower limit may bepaired with any upper limit.

In one or more embodiments, polymer compositions may have a glasstransition temperature (T_(g)) measured by dynamic mechanical analysis(DMA) or DSC in a range having an upper limit selected from any 100° C.,90° C., and 80° C., to a lower limit selected from any of −50° C., −60°C., and −70° C., where any lower limit may be paired with any upperlimit.

In one or more embodiments, polymer compositions may have a meltingtemperature (T_(m)) measured according to ASTM D3418 by DSC in a rangehaving a lower limit selected from any 20° C., 30° C., and 40° C., to anupper limit selected from any of 100° C., 110° C., 120° C., 130° C.,140° C., and 150° C., where any lower limit may be paired with any upperlimit. In some embodiments, polymer compositions may not present a Tm,characterizing a completely amorphous polymer composition.

In one or more embodiments, polymer compositions may have acrystallization temperature (T_(c)) measured according to ASTM D3418 byDSC in a range having a lower limit selected from any 0, 5° C., 10° C.,20° C., and 30° C., and to an upper limit selected from any of 80° C.,90° C., 100° C., 110° C., 120° C., 130° C., 140° C., and 150° C., whereany lower limit may be paired with any upper limit.

In one or more embodiments, polymer compositions may have a heat ofcrystallization measured according to ASTM D3418 by DSC in a rangehaving a lower limit of any of 0, 10, 20, 30, 40, 50, and 60 J/g, and anupper limit of any of 140, 180, 200, 240, and 280 J/g, where any lowerlimit may be paired with any upper limit.

The polymerization conditions result in the production of polymershaving a wide range of molecular weight distribution (MWD). In one ofthe embodiment, the MWD of a polymer obtained within this polymerizationmethod is from about 1 to about 60, with a lower limit of any of 1, 1.5,3, 5, or 10, and an upper limit of any of 10, 20, 30, 40, 50 or 60,where any lower limit can be used in combination with any upper limit.However, depending on the amount of comonomer incorporated, samplesproduced under high-presure conditions show a broad range of MWDs fromabout 1 to 60. Copolymers and terpolymers produced under low-pressureconditions may exhibit number average molecular weights of 1 to 300 kDa,weight average molecular weights of 1 to 1000 kDa and MWDs of 1 to 60.On the other hand, copolymers and terpolymers produced underhigh-pressure conditions may show number average molecular weights of 1to 10000 kDa, weight average molecular weights of 1 to 20000 kDa andMWDs of 1 to 60.

In one or more embodiments, polymer compositions may have a hardness ofthe polymer composition as determined according to ASTM D2240 in a rangehaving a lower limit selected from any 25, 35, and 45 Shore A, to anupper limit selected from any of 80, 90, and 100 Shore A, where anylower limit may be paired with any upper limit.

In one or more embodiments, polymer compositions may have a hardness ofthe polymer composition as determined according to ASTM D2240 in a rangehaving a lower limit selected from any 10, 20, and 30 Shore D, to anupper limit selected from any of 50, 60, and 70 Shore D, where any lowerlimit may be paired with any upper limit.

In one or more embodiments, polymer compositions may have a percentelongation, tensile strength, and modulus as determined according toASTM D368 in a range having a lower limit selected from any 10, 50, and100 percent elongation, to an upper limit selected from any of 500,1000, and 2000 percent elongation, a lower limit selected from any 1, 5,and 10 MPa tensile strength, to an upper limit selected from any of 15,30, 70, 100, 200, and 500 MPa tensile strength, a lower limit selectedfrom any 0.1, 1, 5, 20, and 40 MPa modulus, to an upper limit selectedfrom any of 100, 200, 300, 500, 1000, 2000, 5000, and 10000 MPa modulus,and where any lower limit may be paired with any upper limit.

In one or more embodiments, polymer compositions may have a densityaccording to ASTM D792 in a range having a lower limit selected from anyof 0.75 g/cm³, 0.85 g/cm³, and 0.89 g/cm³, to an upper limit selectedfrom any of 1.1 g/cm³, 1.2 g/cm³, and 1.3 g/cm³, where any lower limitmay be paired with any upper limit.

In one or more embodiments, polymer compositions may have a bio-basedcarbon content, as determined by ASTM D6866-18 Method B, in a rangehaving a lower limit selected from any of 1%, 5%, 10%, and 20%, to anupper limit selected from any of 60%, 80%, 90%, and 100%, where anylower limit may be paired with any upper limit.

In one or more embodiments, polymers may have a long chain branchingfrequency ranging from 0 to 10, such as from a lower limit of any of 1,0.5, 1, or 1.5 and an upper limit of any of 2, 4, 6, 8, or 10, where anylower limit may be paired with any upper limit.

In one or more embodiments, long chain branching average LCBf may becalculated from GPC analysis using a GPC instrument equipped with IR5infrared detector and a four-capillary viscometry detector, both fromPolymer Char. Data collection was performed using Polymer Char'ssoftware. The concentration measured by IR5 detector was calculatedconsidering that the whole area of the chromatogram was equivalent tothe elution of 100% of the mass injected. Average LCBf was thencalculared according to:

${LCBf} = \frac{1000\mspace{14mu} B_{n}R}{M_{w}}$

where R is the molar mass of the repeated unit and is calculated basedon the contribution of monomer and comonomers, considering the molpercentage of each one, determined by NMR. M_(w) is the weight averagemolecular weight and is calculated according to the following equationby means of universal calibration:

$M_{w} = \left\lbrack \frac{\Sigma \left( {N_{i}M_{i}^{2}} \right)}{\Sigma \left( {N_{i}M_{i}} \right)} \right\rbrack$

Average B_(n) constant is calculated according to:

$ = \left\lbrack {\left( {1 + \frac{B_{n}}{7}} \right)^{1/2} + \frac{4B_{n}}{9\pi}} \right\rbrack^{{- 1}/2}$

Average g′ and g constants are calculated according to:

$^{\prime} = \frac{{IV}_{Branched}}{{IV}_{Ltnear}}$^(′) = ^(ɛ)

ϵ is known as the viscosity shielding ratio and is assumed to beconstant and equal to 0.7.

The intrinsic viscosity of the branched samples (IV_(branched)) may becalculated using the specific viscosity (η_(sp)) from the viscometerdetector as follows.

${IV}_{b\tau anched} = {\frac{{\Sigma_{i}\left( \eta_{sp} \right)}_{i}\Delta V_{i}}{SA}\frac{1}{10{KIV}}}$

where SA is sample amount, KIV is viscosity detector constant and thevolume increment (ΔV) is a constant determined by the difference betweenconsecutive retention volumes (ΔV=RV_(i+1)−RV_(i)).

The intrinsic viscosity of the linear counterpart (IV_(linear)) may becalculated using Mark-Houwink equation, whereas the Mark-Houwinkconstants are obtained from the intrinsic viscosity considering theconcentration from Stacy-Haney method as follows. The Stacey-Haney IV(IV_(SH)) is calculated based on Stacy-Haney concentration by

${{IV}_{SH_{i}} = {\frac{1}{KIV}\frac{\eta_{{sp}_{i}}}{C_{{SH}_{i}}}}},$

where C_(SH) is found from

$C_{SHi} = \frac{\left( {{In}\eta_{rel}} \right)_{i}K}{\left( {hv} \right)_{i}^{{a/a} + 1}}$

whereas η_(rel) is the relative viscosity (η_(rel)=η_(sp)+1), (hv)_(i)is the hydrodynamic volume at each elution volume slice from theuniversal calibration curve and the Mark-Houwink exponent, a, wasdefined as 0.725, reference value for a linear polyethylene homopolymerand the constant, K, is calculated according to:

$K = \frac{\frac{SA}{\Delta V}}{\frac{{\Sigma \left( {ln\eta_{rel}} \right)}_{i}}{\left( {hv} \right)_{i}^{{a/a} + 1}}}$

From IV_(SH) _(i) the molecular weight (M_(SH)) on each elution volumeslice is also obtained according to

$M_{SH_{i}} = \frac{hv_{i}}{{IV}_{{SH}_{i}}}$

Plotting IV_(SH) _(i) versus M_(SH) _(i) , both in log scale, leads toMark-Houwink constants k and a for the linear polymer. Finally,IV_(iinear) may be calculated as:

IV_(linear)=kM_(v) ^(a)

where M_(v) is the viscosity average molecular weight by means ofuniversal calibration and the concentration by IR5 infrared detector,and is calculated according to:

$M_{v} = \left\lbrack \frac{\Sigma \left( {N_{i}M_{i}^{a + 1}} \right)}{\Sigma \left( {N_{i}M_{i}} \right)} \right\rbrack^{1/_{a}}$

where N_(i) is the number of ith molecules with molecular weight ofM_(i). The M_(i) is obtained considering the concentration by IR5infrared detector and the hydrodynamic volume from the universalcalibration

$\left( {M_{i} = \frac{hv_{t}}{\frac{1}{KIV}\frac{\eta_{spi}}{c_{{IR}_{i}}}}} \right).$

M_(i) is plotted against the retention volume, the noisy extremes of thecurve are removed and then extrapolated using a third order fitpolynomial. The equation derived from this 3° order fit polynomial isused to calculate the M_(i) as a function of retention volume. In one ormore embodiments, polymers may have a long chain branching frequency,calculated by GPC analysis, ranging from 0 to 10, such as from a lowerlimit of any of 1, 0.5, 1, or 1.5 and an upper limit of any of 2, 4, 6,8, or 10, where any lower limit may be paired with any upper limit.

In one or more embodiments, polymers may have a long chain branchingcontent, measured by ¹³CNMR, ranging from 0 to 10, such as a lower limitof any of 0, 0.2, 0.4, 0.6, 0.8, or 1 and an upper limit of any of 2, 4,6, 8, or 10, where any lower limit may be paired with any upper limit.

In ¹³CNMR analysis, long chain branching (LCB) is defined as any branchwith six or more carbons. Based on ¹³CNMR spectra, LCB content (B₆₊) inbranched polymers is calculated from:

B ₆₊ =S _(3, Polymer) −S _(3, vinyl carbonyl monomers)

where the S₃ peak is positioned at 32.2 ppm on a ¹³CNMR spectrum. Thismethod takes into account both branches (B₆₊) and the chain ends of themain chain, where the effect of the long branches in the vinyl carbonylmonomer is corrected using its ¹³CNMR spectrum, and the effect of chainends can also be corrected with GPC data.

In one or more embodiments, the polymers may have, after thermalfractionation by successive self-nucleation and annealing (SSA), a heatflow versus temperature curve that has 0 to 20 minimums, such as a lowerlimit of any of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minimums and anupper limit of any of 12, 14, 16, 18, or 20 minimums, where any lowerlimit may be paired with any upper limit, where the minimums may beallocated in the temperature ranges of 140-150° C., 130-140° C.,120-130° C., 110-120° C., 100-110° C., 90-100° C., 80-90° C., 70-80° C.,60-70° C., 50-60° C., 40-50° C., 30-40° C., 20-30° C., 10-20° C., and/or0-10° C. Such thermal fractionation may use a temperature protocol (aseries of heating and cooling cycles) to produce a distribution oflamellar crystals whose sizes reflect the distribution of methylsequence lengths in the copolymers and terpolymers. The thermalfractionation may be carried out in a TA Instruments Discovery DSC 2500,under nitrogen. All cooling cycles may be carried out at 5° C./min, andheating cycles may be carried out at 20° C./min. Samples may be heatedfrom 25° C. to 150° C., held at 150° C. for 5 min, cooled to 25° C. andheld at this temperature for 3 min. The sample may subsequently beheated to the first annealing temperature (140° C.), held at thistemperature for 5 min and cooled to 25° C. The sample may then be heatedagain to the next annealing temperature (130° C.), held at thistemperature for 5 min and cooled to 25° C. The procedure may be repeatedin steps of 10° C. until the last annealing temperature (such as, butnot limited to, 0° C.) is reached. Then, the sample may be heated to150° C., at 20° C./min in order to obtain the melting profile.

In one or more embodiments, polymers may have a thermal stability,measured by thermal gravimetric analysis (TGA), where the ratio ofweight loss between 250 to 400° C. relative to the total comonomercontent ranges from 0 to 2, such as a lower limit of any of 0, 0.1, 0.2,0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1, and an upper limit of any of1.2, 1.4, 1.6, 1.8, or 2, where any lower limit may be paired with anyupper limit.

In one or more embodiments, polymers may have a storage modulus at 0° C.of 1 to 50 GPa, such as a lower limit of any of 1, 2, 5, 10, 20, 40, 60,80, or 100 MPa, and an upper limit of any of 200 MPa, 300 MPa, 400 MPa,500 MPa, 700 MPa, 1 GPa, 5 GPa, 10 GPa, 20 GPa, 30 GPa, 40 GPa, or 50GPa where any lower limit may be paired with any upper limit.

In one or more embodiments, polymers may have one to two relaxationmaximums in the tan δ versus temperature plot between −75 to 75° C.where the peak at the higher temperature is designated as α and the peakat lower temperature is designated as β. In one or more embodiments,T_(α) (temperature corresponding to the α peak) can vary between −75 to75° C., such as a lower limit of any of −75, −60, −50, −40, −30, −20,−10, or 0° C., and an upper limit of any of 10, 20, 30, 40, 50, 60, or75° C., where any lower may be paired with any upper limit. In one ormore embodiments, T_(β) (temperature corresponding to the β peak) canvary between −75 to 50° C., such as a lower limit of any of −75, −60,−50, −40, −30, −20, −10, or 0° C., and an upper limit of any of 10, 20,30, 40, or 50° C., where any lower may be paired with any upper limit.

APPLICATIONS

In one or more embodiments, polymer compositions can be used in variousmolding processes, including extrusion molding, injection molding,thermoforming, cast film extrusion, blown film extrusion, foaming,extrusion blow-molding, ISBM (Injection Stretched Blow-Molding), 3Dprinting, rotomolding, pultrusion, and the like, to produce manufacturedarticles.

Polymer compositions in accordance with the present disclosure may alsobe formulated for a number of polymer articles, including the productionof seals, hoses, footwear insoles, footwear midsoles, footwear outsoles,automotive parts and bumpers, sealing systems, hot melt adhesives,films, conveyor belts, sportive articles, rotomolded articles, primers,in civil construction as linings, industrial floors, acousticinsulation, and the like.

In one or more embodiments, polymer compositions may be included inpolymer blends with one or more polymer resins. In some embodiments,polymer compositions may be formulated as a masterbatch that is added ata percent by weight of 1 wt % to 99 wt % to a polymer resin.

The following examples are merely illustrative, and should not beinterpreted as limiting the scope of the present disclosure.

EXAMPLE 1

Ethylene vinyl acetate (EVA) copolymers account for a large portion ofthe ethylene copolymer market and have a range of properties dependenton the vinyl acetate content. An increase in vinyl acetate incorporationresults in a decrease in crystallinity, glass transition temperature,melting temperature, and chemical resistance while increasing opticalclarity, impact and stress crack resistance, flexibility and adhesion.In this example, ethylene-based polymers incorporating various amountsof vinyl acetate and a vinyl carbonyl monomer VeoVa™ 10 from HEXION™ (amixture of isomers of vinyl esters of versatic acid having a carbonnumber of 10) were produced to assay a number of polymer properties forthe resulting compositions.

Ethylene (99.95%, Air Liquide, 1200 psi), VeoVa™ 10 (Hexion) and2,2′-azobisisobutyronitrile (AIBN, 98% Sigma Aldrich) were used asreceived. Dimethyl carbonate (DMC, anhydrous 99%, Sigma Aldrich), andvinyl acetate (99%, Sigma Aldrich) were distilled before use and storedunder nitrogen.

Synthesis of terpolymers with ethylene, vinyl acetate and VeoVa™ 10(Samples A1-A5)

Polymer compositions were prepared using a free radical polymerizationof the comonomer mixtures in solution by combining 80 g of dimethylcarbonate (DMC), 9.97 or 14.98 g of vinyl acetate, 13.5 or 11.48 gVeoVa™ 10, and 0.1 g of azobisisobutyronitrile (AIBN) to a Parr reactor.The reactor was sealed and flushed 3 times with ethylene with 1000 psiof pressure while stirring. The system was then heated at 70° C. at anethylene pressure of 1200 psi and stirred for 2 hours. The reactionmixture was collected and the reactor was washed with THF at 60° C. Thesolvent in the reaction mixture and wash was removed by rotaryevaporation. The resulting polymer was dissolved in THF and precipitatedinto cold methanol, then vacuum filtered.

EXAMPLE 2

Ethylene-based polymers incorporating various amounts of vinyl pivalate,vinyl laurate and vinyl 4-tert-butylbenzoate were produced to assay anumber of polymer properties for the resulting compositions.

Ethylene (99.95%, Air Liquide, 1200 psi) and azobisisobutyronitrile(AIBN, 98% Sigma Aldrich) were used as received. Dimethyl carbonate(DMC, anhydrous 99%, Sigma Aldrich), vinyl acetate (99%, Sigma Aldrich),vinyl pivalate (99%, Sigma Aldrich), vinyl laurate (99%, Sigma Aldrich)and vinyl 4-tert-butylbenzoate (99%, Sigma Aldrich) were distilledbefore use and stored under nitrogen.

Synthesis of terpolymers with ethylene, vinyl acetate and vinylpivalate, vinyl laurate and vinyl 4-tert-butylbenzoate (Samples B1-B3)

Polymer compositions were prepared using a free radical polymerizationof the comonomer mixtures in solution by combining 80 g of dimethylcarbonate (DMC), 9.3 g of vinyl acetate and 13.9 g of vinyl pivalate or24.4 g of vinyl laurate or 22 g vinyl 4-tert-butylbenzoate, and 0.1 g ofazobisisobutyronitrile (AIBN) to a Parr reactor. The reactor was sealedand flushed 3 times with ethylene with 1000 psi of pressure whilestirring. The system was then heated at 70° C. at an ethylene pressureof 1200 psi and stirred for 2 hours. The reaction mixture was collectedand the reactor was washed with THF at 60° C. The solvent in thereaction mixture and wash was removed by rotary evaporation. Theresulting polymer was dissolved in THF and precipitated into coldmethanol, then vacuum filtered.

EXAMPLE 3

Ethylene-based polymers incorporating various amounts of vinyl acetateand a vinyl carbonyl monomer VeoVa™ 10 from HEXION™, a mixture ofisomers of vinyl esters of versatic acid having a carbon number of 10under high-pressure conditions were produced to assay a number ofpolymer properties for the resulting compositions.

Ethylene, VeoVa™ 10 (Hexion), tertbutylperoxy-2-ethylhexanoate, heptane(99%, Sigma Aldrich), and vinyl acetate (99%, Sigma Aldrich) were usedas received.

Synthesis of terpolymers with ethylene, vinyl acetate and VeoVa™ 10 wereperformed under high-pressure conditions (Samples D1-D15).

Polymer compositions were prepared using a continuous free radicalpolymerization™ 10, heptane and tertbutylperoxy-2-ethylhexanoate into ahigh-pressure reactor. Before each round of polymerization, the reactorwas purged five times with 2200-2300 bars of ethylene. Each reactionbegan by heating the reactor to 200° C. and feeding ethylene to apressure of 1900-2000 bar. A continuous flow of ethylene with a rate of2000 g/hr was then fed into the reactor. Once the targeted pressure andstable ethylene flow was achieved, the comonomers were added to thereactor. The mixture of initiator and heptane was introduced to thesystem at a flow rate of 2 mL/hr. The reaction mixtures was collectedand the reactor was washed with xylene at 145° C. The resulting polymerwas dissolved in xylene and precipitated into cold methanol, then vacuumfiltered.

EXAMPLE 4

In this example, an ethylene-based polymer was produced by incorporatingtrimethylsilyl-protected methyl vinyl glycolate to assay a number ofpolymer properties for the resulting compositions.

Ethylene (99.95%, Air Liquide, 1200 psi) and azobisisobutyronitrile(AIBN, 98% Sigma Aldrich) were used as received. Dimethyl carbonate(DMC, anhydrous 99%, Sigma Aldrich) was distilled before use and storedunder nitrogen.

Synthesis of copolymer with ethylene and trimethylsilyl-protected methylvinyl glycolate (Sample E1)

8 g trimethylsilyl-protected methyl vinyl glycolate, 80 g dimethylcarbonate and 0.1 g of azobisisobutyronitrile were added to a 300 mLParr reactor. The reactor was sealed and flushed three times with 1000psi pressure of nitrogen while stirring. The system was then heated, at70° C. at an ethylene pressure of 1200 psi and allowed to stir for thedesired time. The reaction mixture was collected and the reactor waswashed with THF at 60° C. The solvent in the reaction mixture and washwas removed by rotary evaporation. The resulting polymer was dissolvedin THF and precipitated into cold methanol, then vacuum filtered.

EXAMPLE 5

In this example, an ethylene-based polymer was produced by incorporatingvinyl acetate and trimethylsilyl-protected methyl vinyl glycolate toassay a number of polymer properties for the resulting compositions.

Ethylene (99.95%, Air Liquide, 1200 psi) and azobisisobutyronitrile(AIBN, 98% Sigma Aldrich) were used as received. Dimethyl carbonate(DMC, anhydrous 99%, Sigma Aldrich) and vinyl acetate (99%, SigmaAldrich) were distilled before use and stored under nitrogen.

Synthesis of terpolymer with ethylene, vinyl acetate andtrimethylsilyl-protected methyl vinyl glycolate (Sample E2)

5 g trimethylsilyl-protected methyl vinyl glycolate, 15 g vinyl acetate,80 g dimethyl carbonate and 0.1 g of azobisisobutyronitrile were addedto a 300 mL Parr reactor. The reactor was sealed and flushed three timeswith 1000 psi pressure of nitrogen while stirring. The system was thenheated, at 70° C. at an ethylene pressure of 1200 psi and allowed tostir for the desired time. The reaction mixture was collected and thereactor was washed with THF at 60° C. The solvent in the reactionmixture and wash was removed by rotary evaporation. The resultingpolymer was dissolved in THF and precipitated into cold methanol, thenvacuum filtered.

EXAMPLE 6

In this example, ethylene-based polymers incorporating by incorporatingmethyl vinyl glycolate under high pressure conditions were produced toassay a number of polymer properties for the resulting compositions.

Ethylene and tertbutylperoxy-2-ethylhexanoate were used as received.Toluene (99%, Sigma Aldrich) was distilled before use and stored undernitrogen.

Synthesis of copolymers with ethylene and methyl vinyl glycolate underhigh pressure conditions (Samples E3-E4)

Polymer compositions were prepared using a batch free radicalpolymerization of the comonomer mixture by combining 0.45 g methyl vinylglycolate, toluene and various amounts oftertbutylperoxy-2-ethylhexanoate into a high-pressure reactor. Beforeeach round of polymerization, the reactor was purged five times with2200-2300 bars of ethylene. Each reaction began by heating the reactorto 200° C. and feeding ethylene to a pressure of 1900-2000 bar. Once thetargeted pressure and stable ethylene flow was achieved, the comonomerswere added to the reactor. The mixture of initiator and toluene was thenintroduced to the system. The reaction mixtures were collected, and thereactor was washed with xylene at 145° C. The resulting polymer wasdissolved in xylene and precipitated into cold methanol, then vacuumfiltered.

Polymer Characterization

Twenty-seven samples of ethylene-based polymers denoted A1-A5, B1-B3,D1-D15 and E1-E4 were purified and characterized. The ethylene-basedpolymers contained varying amounts of both vinyl acetate and a vinylcarbonyl monomer.

TABLE 1 Reaction Summary with NMR and GPC Results for Examples 1 to 6Vinyl 4- Methyl Trimethylsilyl- Vinyl VeoVa ™ Vinyl Vinyl tert-butylVinyl Protected Methyl Acetate 10 Pivalate Laurate bezoate GlycolateVinyl Glycolate M_(w) M_(n) Conversion Samples (wt %)^(a,b) (wt %)^(a,b)(wt %)^(a,b) (wt %)^(a,b) (wt %)^(a,b) (w %)^(a,b) (w %)^(a,b) (kDa)(kDa) MWD (%) A1 11.4 23.4 — — — — — 27.0 13.0 2.1 — A2 10.2 18.7 — — —— — 25.9 11.3 2.3 — A3 9.1 22.2 — — — — — 20.3 10.1 2.0 — A4 14.4 26.1 —— — — — 18.7 8.3 2.3 — A5 14.7 22.6 — — — — — 22.6 10.3 2.2 — B1 11.2 —16.7 — — — — 23.4 8.1 2.9 — B2 9.5 — — 27.7 — — — 22.3 5.1 4.4 — B3 16.0— — — 47.4 — — 11.9 4.2 2.8 — D1 — 3.3 — — — — — 1173.3 67.7 17.3 17.5D2 — 4.6 — — — — — 996.7 61.1 16.3 14.5 D3 — 8.3 — — — — — 537.6 48.911.0 15.8 D4 — 10.8 — — — — — 425.1 41.9 10.1 8.2 D5 — 19.2 — — — — —220.6 22.7 9.7 6.7 D6 — 25.5 — — — — — 207.2 24.3 8.5 4.8 D7 4.8 23.9 —— — — — 64.2 19.0 3.4 4.2 D8 10.2 19.7 — — — — — 55.5 16.9 3.3 5.9 D915.7 14.2 — — — — — 57.6 20.2 2.9 15.6 D10 20.5 9.9 — — — — — 55.1 17.33.2 16.4 D11 25.0 1.9 — — — — — 75.3 19.8 3.8 14.2 D12 29.1 — — — — — —52.8 15.3 3.4 16.9 D13 — 22.4 — — — — — 52.1 10.7 4.9 5 D14 21.2 8.4 — —— — — 48.6 11.6 4.2 6 D15 25.8 5.0 — — — — — 56.5 10.5 5.4 12.2 E1 — — —— — — 10.3 2.8 1.0 2.8 — E2 30.1 — — — — — 1.1 3.6 1.3 2.8 — E3 — — — —— 0.89 — 184.7 6.1 30.5 — E4 — — — — — 5.01 — 97.3 3.9 25.1 — M1 28^(a)— — — — — — 78.5 13.5 5.8 — M2 28^(a) — — — — — — 59.3 14.5 4.1 —^(a)Determined from ¹H NMR; ^(b)Determined from ¹³C NMR; MW and MWD arefound using a GPC equipped with a viscometer detector. Conversion iscalculated using mass flow of monomers and produced polymer.

Table 1 provides a summary of the gel permeation chromatography (GPC)and nuclear magnetic resonance (NMR) data for all polymers synthesizedand two comparative commercial EVA samples M1-M2.

For the polymer samples containing the vinyl carbonyl monomers,incorporation was determined using quantitative ¹³C NMR, since the ¹HNMR contained significant overlap in both the carbonyl and alkyl regionsfor accurate integration. The carbonyl peaks not observed in pure EVA¹³C NMR were identified as coming from the branched vinyl carbonylmonomer units and used to calculate the weight percent of the comonomer.

With particular respect to FIG. 1, the full ¹³C NMR spectra (TCE-D_(2,)393.1 K, 125 MHz) for the VeoVa™ acid 10 monomer and representativesamples A2 and M1 are shown. There is evidence of incorporation of thebranched vinyl ester seen in both the carbonyl (170-180 ppm) and alkylregions (0-50 ppm). The spectra show a significant increase in the peaksindicative of carbonyl carbons and long alkyl chains within the branchedvinyl ester. General peak assignments are also shown in FIG. 1. Whencomparing spectra of the VeoVa™ acid 10 monomer and the polymer A2, thepolymer spectrum exhibits a disappearance of the vinyl peaks andappearance of peaks corresponding to all three comonomers studied(ethylene, vinyl acetate, and VeoVa™ acid 10). The abundant number ofpeaks in both regions may be due to the mixture of isomers in the VeoVa™acid 10 monomer, and the appearance of these peaks in the polymersamples validates the formation of the respective terpolymer.

Further evidence of the incorporation of the VeoVa™ acid 10 monomer isdemonstrated in FIG. 2 showing the ¹H NMR spectra (TCE-D₂, 393.2 K, 500MHz) for the polymer samples A2 and M1. The spectra exhibit peaks forvinyl acetate and ethylene as well as additional peaks in the alkylregion (0.5-1.5 ppm) indicative of the long alkyl chains on the branchedvinyl ester monomer.

The ¹H NMR spectrum (TCE-D₂, 393.2 K, 500 MHz) for A2 and M1 are shownwith a number of relevant peak assignments. FIG. 2 shows that there isoverlap between vinyl acetate and the branched vinyl ester monomer unitsaround the peaks slightly upfield from 5 ppm. If these peaks were purelythe methine of ethyl acetate, the integral ratio between the 5 ppm peaksand the peak around 2 ppm (methyl from vinyl acetate) would be 1:3.However, the integral ratio is 1:1, indicating that the methines of bothvinyl acetate and branched vinyl ester overlap, generating the broadenedpeaks around 5 ppm. Relative intensity of the peaks found in ¹H NMR and¹³C NMR spectra are used to calculate monomer incorporation of vinylester and VeoVa™ 10 in the co-/terpolymers.

With particular respect to FIG. 3, the full ¹³C NMR spectra (TCE-d₂,393.1 K, 125 MHz) for samples E1 and E2 are shown. There is evidence ofincorporation of the trimethylsilyl-protected methyl vinyl glycolateseen in the 175 ppm, 125 ppm and 50 ppm regions. General peakassignments are also shown in FIG. 3.

Further evidence of the incorporation of the trimethylsilyl-protectedmethyl vinyl glycolate monomer is demonstrated in FIG. 4 showing the ¹HNMR spectra (TCE-d, 393 K, 500 MHz) for the polymer samples E1 and E2.The spectra exhibit peaks for vinyl acetate and ethylene as well asadditional peaks (1.8 ppm and 3.8 ppm) indicative of thetrimethylsilyl-protected methyl vinyl glycolate monomer.

With particular respect to Table 1, a broad range of conversions areobtained for each polymer. The degree of conversion duringpolymerization will affect the degree of branching and topology of thechains, altering properties of the polymers.

With particular respect to FIG. 5, a gel permeation chromatograph isshown for the samples, from which the molecular weights anddistributions of the terpolymers were derived. The GPC experiments werecarried out in a gel permeation chromatography coupled with tripledetection, with an infrared detector IR5 and a four bridge capillaryviscometer, both from PolymerChar and an eight angle light scatteringdetector from Wyatt. It was used a set of 4 column, mixed bed, 13 μmfrom Tosoh in a temperature of 140° C. The conditions of the experimentswere: concentration of 1 mg/mL, flow rate of 1 mL/min, dissolutiontemperature and time of 160° C. and 90 minutes, respectively and aninjection volume of 200 μL. The solvent used was TCB (Trichloro benzene)stabilized with 100 ppm of BHT.

The polymers A1-A5 containing VeoVa™ 10 exhibit molecular weightsranging for 10 to 30 kDa and MWD around 2. Similar MWD is observed forpolymers B1-B3 and E1-E2. While the traces of the terpolymers aresimilar to that of the comparative commercial samples (M1-M3), theydiffer in their molecular weight distribution, the commercial gradesshow a broader range of molecular weights with MWD ranging from 4-6.However, depending on the amount of comonomer incorporated, samplesproduced under high-pressure conditions (polymers D1-D15 and E3-E4) showa broad range of MWDs from about 2 to 31. Copolymers and terpolymersproduced under low-pressure conditions usually exhibit number averagemolecular weights 1 to 300 kDa, weight average molecular weights of 1 to1000 kDa and MWDs of 1 to 60. On the other hand, copolymers andterpolymers produced under high-pressure conditions typically shownumber average molecular weights of 1 to 10000 kDa, weight averagemolecular weights of 1 to 20000 kDa and MWDs of 1 to 60. Due to presenceof high molecular weight chains in these polymers, they can show uniqueproperties compared to their low MWD counterparts (such as higher meltstrength, ESCR, impact strength, etc.).

With particular respect to FIGS. 6A-6C, two-dimensional liquidchromatography (2D-LC) chromatographs of polymers D13-D15 arerespectively shown. The 2D-LC system analyzed these copolymer andterpolymers using high performance liquid chromatography (HPLC) and GPCinstruments. 2D-LC measurements were performed using a PolymerChar 2D-LChigh-temperature chromatograph (Valencia, Spain×I.D., 5 μm particlesize) and a PLgel Olexis GPC column (300×7.5 mm L×I.D., 13 μm particlesize). The sample loop for 2D-LC contains a volume of 200 μL. Allexperiments were performed at 160° C. Detection was realized with afixed wavelength infrared (IR) detector (IR6, PolymerChar), withdetection capabilities (bandpass filters) for overall polymerconcentration, CH2, CH3 and C═O. GPC elution times were calibrated withpolystyrene (EasiCal PS-1, Agilent, Waldbronn, Germany). The calibrationwas performed in GPC mode and applied to 2D-LC results as well. HPLCmobile phase was 1-decanol (Merck, Darmstadt,Germany)/1,2-dichlorobenzene (ODCB, Acros Organics, Schwerte, Germany),with a flow rate of 0.01 mL/min. Gradient conditions: 0-200 min: pure1-decanol, 200-700 min: linear gradient of 1-decanol to ODCB, 700-1100min: pure ODCB. Afterwards, the column was flushed with 1-decanol at 0.8mL/min for 40 min to reestablish the adsorption equilibrium. GPC mobilephase was 1,2-dichlorobenzene (ODCB, Acros Organics, Schwerte, Germany)with a flow rate of 1.5 mL/min. HPLC eluent from the fractionation valvesample loops (100 μL) was injected into the GPC every 10 min. Sampleconcentrations were approximately 8 mg/mL, 6 mL mobile phase wereautomatically added to the sample vials (containing weighed polymer) bythe autosampler, while simultaneously flushing them with nitrogen. Thesamples were dissolved for 1 h, under shaking, prior to injection. Forcalibration of HPLC elution times of EVA, EVA samples with average vinylacetate contents of 70, 50, 30, 14 and 5 wt % were used. All sampleswere mixed (similar concentration, ca. 2 mg) and analyzed in a single2D-LC run. For calibration of HPLC elution times of VeoVA, a similarapproach with samples D1-D6 was used. Except for the low molecularweight fraction, all polymers show a uniform distribution of vinylacetate and VeoVa™ 10 over the molar mass distribution. Concentration ofvinyl acetate and VeoVa™ 10 in the polymer chains varies between 10 to65 wt % in these polymers.

To analyze the long chain branching frequency (LCBf) the samples wereanalyzed using a GPC instrument equipped with IR5 infrared detector anda four-capillary viscometry detector, the results of which are shown inTable 2.

TABLE 2 Summary of LCBf Results Samples g′ g B_(n) LCBf D5 0.715 0.6208.048 1.284 D6 0.663 0.556 11.426 1.117 D7 0.878 0.830 2.173 0.547 D80.852 0.795 2.815 0.717 D10 0.927 0.897 1.155 0.334 D12 0.934 0.9071.020 0.318 D14 0.948 0.926 0.787 0.270 D15 0.853 0.797 2.779 0.634

The content of long chain branching on several polymer samples wasmeasured ¹³CNMR and the method described herein, the results of whichare summarized in Table 3 below.

TABLE 3 Summary of LCB Content Results Samples B₆₊ D1 1.725 D5 1.010 D71.065 D10 1.338 D12 1.973 D14 1.312 D15 1.182

Thermal property analysis of the polymers was carried out usingDifferential Scanning calorimetry (DSC), and Dynamic Mechanical Analysis(DMA). With particular respect to FIG. 7A-7C, DSC analysis of EVA andterpolymer samples is shown in FIG. 7A, where FIGS. 7B-7C provide anexpanded view of the peaks in FIG. 7A. During DSC analysis, thesesamples were equilibrated at 140° C. for 5 min and the measurementproceeded at a cooling rate of 10° C./min followed by equilibration at−50.0° C. and a heating rate of 10° C./min up to 140° C.

Table 4 summarizes the DSC and DMA data. When comparing the polymerscontaining the branched vinyl ester comonomer with the comparativesamples, the crystallization temperature appears most affected from theincorporation of branched vinyl ester comonomers. This trend is expectedfrom the crystallization interruption caused by the branched groupsarising in the polymer from introduction of the vinyl ester comonomers.Introduction of vinyl carbonyl comonomers into a copolymer of ethyleneand vinyl acetate may result in a terpolymer with a different morphologyfrom EVA copolymers. This monomer may disrupt the structural regularityand the polymer's ability to pack into a crystalline state.Consequently, by increasing the amorphous regions the T_(g), T_(m) andT_(c) of the obtained polymer may decrease.

Heat of crystallization (ΔH), crystallization temperature, meltingtemperature for polymers made in Examples 1 to 3 and commercial EVAsamples is shown in Table 4. The analyses were carried out undernitrogen in a TA Q2000 instrument. A sample was heated to 160° C. at 10°C./min, held at this temperature for 1 minute, cooled down to −20° C. at10° C./min and held at this temperature for 1 minute. Then, the samplewas heated up to 160° C. at 10° C./min. The cooling and second heatingcurves were recorded, analyzed by setting the baseline endpoints and thecrystallization peak temperature, melting peak temperature and ΔH wereobtained.

TABLE 4 DSC, DMA, MFI and Density results for Example 1, 2 and 3Endothermic Den- T_(c) peak T_(m) peak ΔH MFI sity Samples (° C.) (° C.)(J/g) Tg (° C.) (g/10 min) (g/cm³) A1 46 70 12.4 −24 — — A2 40 66 9.9−25 — — A3 31 51 1.5 −34 — — A4 34 59 1.6 −35 — — A5 36 58 6.3 −41 — —B1 44 63 19.9 −17 — — B2 43 56 17.2 −24 — — B3 18 39 10.7 9.2 — — D1 100111 140 50 to −5  — — D2 99 112 136 50 to −10 — — D3 95 107 123 47 to−10 — — D4 92 106 117 45 to −15 — — D5 83 97 97 50 to −20 — — D6 79 9383 −20 — — D7 67 84 69 −24 — — D8 63 80 62 −24 — — D9 62 78 61 −23 — —D10 58 75 57 −22 — — D11 59 76 63 −21 — — D12 53 72 60 −20 26.5 — D13 7490 96 −18 118 0.9129 D14 60 77 64 −22 150 0.9290 D15 57 75 56 −16 950.9321 M1 52 73 19.2 −19 — — M2 53 74 21.9 −20 — — M3 86 101 113 6.3 — —

Glass transition temperature (T_(g)) for the samples were determinedfrom the measurement of Tan δ peak maximum of the samples during DMAmeasurements using a TA 800 DMA instrument in the tensile mode. Thinfilms made of each samples were cooled to −150° C. and theirviscoelastic response was evaluated through temperature sweep with arate of 3° C./min while a preload force of 0.01 N with a frequency of 1Hz and amplitude of 30 μm was aplied. Storage modulus, loss modulus, andtan δ (ratio of storage to loss modulus) was recorded as a function oftemperature. A reference temperature of 0° C. was selected to comparethe storage modulus of the samples. In the range of −75° C. to 75° C.the samples showed one to two maximums in the tan δ versus temperatureplot. In the case where there is one peaks in the range of −75° C. to75° C., it is designated as the α peak. In the case where there is twopeaks in the range of −75° C. to 75° C. , the maximum at highertemperature is designated as the α relaxation while the maximum at thelower temperature is marked as the β relaxation. Different polymermorphology is also discernible in DMA results. With particular respectto FIGS. 8A-8B, DMA of D2-D7, D9, and D11 are shown. D2-D6 show a broadrelaxation from −50 to 75° C. By increasing the amount of branched vinylester comonomer, the intensity of the α relaxation peak decreases whilethe intensity of the β relaxation peak increases. D4 shows the broadestrelaxation in this region. Similar to commercial EVA samples, samplesD7, D9, and D11 show single relaxation in this range.

With particular respect to Table 4, copolymers and terpolymers producedin the Examples also show a broad range of MFR and densities. Table 5summarizes the storage modulus results at 0° C. for Example 3, whichdepending on different morphologies, cover a broad range of values.

TABLE 5 Storage modulus results for Example 3 Samples Storage Modulus at0° C. (MPa) D1 582 D2 465 D3 366 D4 354 D5 191 D6 76 D7 40 D8 33 D9 31D10 26 D11 43 D12 26

Thermal degradation of the polymers was studied by thermal gravimetricanalysis (TGA) under a nitrogen atmosphere. The sample is place in a TAQ500 TGA instrument and heated from 25 to 700° C. with heating rate of20° C./min. Weight loss as a function of temperature is recorded. Withparticular respect to FIG. 9A-9B, TGA of D7-D10 is shown. All thesepolymers contain about 30 wt % comonomers. The first weight loss inthermogram of these polymers (at lower temperatures) is related toseparation of acidic groups (acetic acid or versatic acid) from thepolymer. The second weight loss at higher temperatures corresponds todegradation of the polymer backbone. Replacing vinyl acetate with VeoVa™10 during high pressure polymerization leads to polymers that are morestable and show less weight loss at lower temperatures. FIG. 9B showsthat as the amount of VeoVa™ 10 in the copolymers and terpolymersincreases, the intensity of the first weight lost (ratio of the amountof first weight loss divided by the total comonomer content) decreasesand the copolymer and terpolymers become more thermally stable. Thesecond degradation occurs after 400° C., where the carbon-carbon bondsin the polymer backbone begins to degrade.

Samples were also subjected to thermal fractionation. Thermalfractionation employs a temperature protocol (a series of heating andcooling cycles) to produce a distribution of lamellar crystals whosesizes reflect the distribution of methyl sequence lengths in thecopolymers and terpolymers. The thermal fractionation was carried out ina TA Instruments Discovery DSC 2500, under nitrogen. All cooling cycleswere carried out at 5° C./min and heating cycles were carried out at 20°C./min. Samples were heated from 25° C. to 150° C., held at 150° C. for5 min, cooled to 25 C.° and held at this temperature for 3 min. Thesample was subsequently heated to the first annealing temperature (140°C.), held at this temperature for 5 min and cooled to 25° C. The samplewas heated again to the next annealing temperature (130° C.), held atthis temperature for 5 min and cooled to 25° C. The procedure wasrepeated until the last annealing temperature (70° C.), in steps of 10°C. Then, the sample was heated to 150° C., at 20° C./min in order toobtain the melting profile. Annealing temperatures include: 140° C.,130° C., 120° C., 110° C., 100° C., 100° C., 90° C., 80° C. and 70° C.The thermal fractionation by SSA results in FIGS. 10A-10B.

Although only a few example embodiments have been described in detailabove, those skilled in the art will readily appreciate that manymodifications are possible in the example embodiments without materiallydeparting from this invention. Accordingly, all such modifications areintended to be included within the scope of this disclosure as definedin the following claims. In the claims, means-plus-function clauses areintended to cover the structures described herein as performing therecited function and not only structural equivalents, but alsoequivalent structures. Thus, although a nail and a screw may not bestructural equivalents in that a nail employs a cylindrical surface tosecure wooden parts together, whereas a screw employs a helical surface,in the environment of fastening wooden parts, a nail and a screw may beequivalent structures. It is the express intention of the applicant notto invoke 35 U.S.C. § 112(f) for any limitations of any of the claimsherein, except for those in which the claim expressly uses the words‘means for’ together with an associated function.

What is claimed:
 1. A polymer composition, comprising: a polymerproduced from ethylene, and one or more vinyl carbonyl monomers havingthe general structure (I):

where R¹, R² and R³ are independently selected from a group consistingof hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,substituted alkoxy, alkenyl, substituted alkenyl, alkynyl, substitutedalkynyl, aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substitutedcycloalkyl, substituted cycloalkoxy, substituted aryl, and substitutedheterocycles; and Y and Z are independently selected from a groupconsisting of O, (CR^(5a)R^(5b)), (CHR^(6a))—R^(6b), phenylene, CH—OR⁷,and NR⁸, wherein R^(5a), R^(5b), R^(6a), R^(6b), and R⁸ areindependently selected from a group consisting of hydrogen, halogen,CH₂, and alkyl, and wherein R⁷ is independently selected from a groupconsisting of hydrogen; halogen; hydroxyl; alkyl; linear ether; cyclicether; Si(R⁹)₃, wherein R⁹ is independently selected from a groupconsisting of hydrogen, halogen, and alkyl; and (C═O)—R¹⁰, wherein R¹⁰is an alkyl; and R⁴ is independently selected from a group consisting ofhalogen, hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy,alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl,(heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substitutedcycloalkoxy, substituted aryl, and substituted heterocycles; where thepolymer composition has a number average molecular weight (M_(n))ranging from 5 kDa to 10000 kDa obtained by GPC.
 2. The polymercomposition of claim 1, wherein Y or Z is CH—OR⁷, wherein R⁷ is selectedfrom a group consisting of hydrogen; alkyl; Si(R⁹)₃, wherein R⁹ isselected from a group consisting of hydrogen, halogen, and alkyl; linearether; cyclic ether; and (C═O)—R¹⁰, wherein R¹⁰ is an alkyl.
 3. Thepolymer composition of claim 1, wherein the one or more vinyl carbonylmonomers comprise a mixture of isomers.
 4. The polymer composition ofclaim 1, wherein Y is O.
 5. The polymer composition of claim 1, whereinR¹, R², and R³ are hydrogen.
 6. The polymer composition of claim 1,wherein the general structure of Z is C(R^(5a)R^(5b)), and whereinR^(5a) and R^(5b) are each independently selected from a groupconsisting of hydrogen, halogen, and alkyl.
 7. The polymer compositionof claim 1, wherein the polymer composition further comprises one ormore diene monomers.
 8. The polymer composition of claim 7, wherein theone or more diene monomers are present at a percent by weight of thepolymer composition (wt %) ranging from greater than 0.01 wt % to 50 wt% measured by ¹H NMR and/or ¹³C NMR.
 9. The polymer composition of claim7, wherein the one or more diene monomers are selected from the groupconsisting of dicyclopentadiene, 1,3-pentadiene and combinationsthereof.
 10. The polymer composition of claim 1, wherein the one or morevinyl carbonyl monomers are present at a percent by weight of thepolymer composition (wt %) ranging from greater than 0.01 wt % to 90 wt% measured by ¹H NMR and/or ¹³C NMR.
 11. The polymer composition ofclaim 1, wherein the crystallinity of the polymer composition is in therange of 0.1% to 80% measured by DSC, according to ASTM D3418, or WAXD.12. The polymer composition of claim 1, wherein the glass transitiontemperature of the polymer composition is in the range of −70° C. to100° C. measured by DMA or DSC.
 13. The polymer composition of claim 1,wherein the melting temperature of the polymer composition, according toASTM D3418, is in the range of 0° C. to 150° C. measured by DSC.
 14. Thepolymer composition of claim 1, wherein the crystallization temperatureof the polymer composition, according to ASTM D3418, is in the range of0° C. to 150° C. measured by DSC.
 15. The polymer composition of claim1, wherein the long chain branching frequency ranges from 0 to 10, asmeasured by GPC.
 16. The polymer composition of claim 1, wherein thelong chain branching content ranges from 0 to 10, as measured by ¹³CNMR.17. The polymer composition of claim 1, wherein the polymer has a heatflow versus temperature curve, measured by thermal fractionation bysuccessive self-nucleation and annealing with 10° C. steps, that has 0to 20 minimums.
 18. The polymer composition of 17, wherein the minimumsare in a temperature range of 0 to 150° C.
 19. The polymer compositionof claim 1, wherein a ratio of a first weight loss, between 250 to 400°C., relative to a total comonomer content, ranges from 0 to
 2. 20. Thepolymer composition of claim 1, wherein the polymer has a storagemodulus at 0° C. ranging from 0.1 MPa to 50 GPa.
 21. The polymercomposition of claim 1, wherein the polymer has 1 to 2 relaxationmaximums in a tan δ versus temperature plot between −75 to 75° C. 22.The polymer composition of claim 21, wherein T_(α) varies between −75and 75° C.
 23. The polymer composition of claim 22, wherein T_(β) variesbetween −75 and 50° C.
 24. The polymer composition of claim 1, whereinthe hardness of the polymer composition as determined according toASTMD2240 is in the range of 35 to 90 Shore A.
 25. The polymercomposition of claim 1, wherein the hardness of the polymer compositionas determined according to ASTMD2240 is in the range of 20 to 60 ShoreD.
 26. The polymer composition of claim 1, wherein the MFR according toASTM D1238 at 190° C./2.16 kg is in the range of 0.01 g/10 min to 1000g/10 min.
 27. The polymer composition of claim 1, wherein the densityaccording to ASTM D1505/D792 is in the range of 0.85 g/cm³ to 1.3 g/cm³.28. The polymer composition of claim 1, wherein the bio-based carboncontent according to ASTM D6866-18 is in the range of 1% to 100%. 29.The polymer composition of claim 1, wherein the polymer composition isprepared by solution phase polymerization.
 30. The polymer compositionof claim 1, wherein the polymer composition is prepared by low pressurepolymerization.
 31. The polymer composition of claim 1, wherein thepolymer composition is prepared by high-pressure polymerization.
 32. Thepolymer composition of claim 1, wherein the polymer is produced with theaddition of one or more initiators for free-radical polymerization addedat a percent by weight of the total composition ranging from 10⁻⁷ wt %to 5 wt %.
 33. The polymer composition of claim 1, wherein the one ormore vinyl carbonyl monomers have the general structure (II):

wherein R¹¹, R¹², and R¹³ have a combined carbon number in the range ofC3 to C20 and the polymer composition has a number average molecularweight (M_(n)) ranging from 5 kDa to 10000 kDa obtained by GPC.
 34. Thepolymer composition of claim 33, wherein the one or more vinyl carbonylmonomers have the general structure (III):

wherein R¹⁶ and R¹⁷ have a combined carbon number of 6 or 7 and thepolymer composition has a number average molecular weight (M_(e))ranging from 5 kDa to 10000 kDa obtained by GPC.
 35. The polymercomposition of claim 1, wherein the polymer composition furthercomprises a vinyl acetate monomer.
 36. The polymer composition of claim35, wherein the polymer composition comprises a vinyl acetate monomercontent at a percent by weight (wt %) of the polymer composition rangingfrom greater than 0.01 wt % to 90 wt % measured by ¹H NMR and/or ¹³CNMR.
 37. A polymer composition, comprising: a polymer produced fromethylene, and one or more vinyl carbonyl monomers having the generalstructure (I):

where R¹, R² and R³ are independently selected from a group consistingof hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,substituted alkoxy, alkenyl, substituted alkenyl, alkynyl, substitutedalkynyl, aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substitutedcycloalkyl, substituted cycloalkoxy, substituted aryl, and substitutedheterocycles; and Y and Z are independently selected from a groupconsisting of O, (CR^(5a)R^(5b)), (CHR^(6a))—R^(6b), phenylene, CH—OR⁷,and NR⁸, wherein R^(5a), R^(5b), R^(6a), R^(6b), and R⁸ areindependently selected from a group consisting of hydrogen, halogen,CH₂, and alkyl, and wherein R⁷ is independently selected from a groupconsisting of hydrogen; halogen; hydroxyl; alkyl; linear ether; cyclicether; Si(R⁹)₃, wherein R⁹ is independently selected from a groupconsisting of hydrogen, halogen, and alkyl; and (C═O)—R¹⁰, wherein R¹⁰is an alkyl; and R⁴ is independently selected from a group consisting ofhalogen, hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy,alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl,(heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substitutedcycloalkoxy, substituted aryl, and substituted heterocycles wherein whenY is O, the combined carbon count of Z and R⁴ is less than 8 or morethan
 9. 38. A polymer composition, comprising: a polymer produced fromethylene, and one or more vinyl carbonyl monomers having the generalstructure (IV):

wherein R¹⁴ and R¹⁵ are independently selected from the group consistingof hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,substituted alkoxy, alkenyl, substituted alkenyl, alkynyl, substitutedalkynyl, aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substitutedcycloalkyl, substituted cycloalkoxy, substituted aryl, substitutedheterocycles, and Si(R⁹)₃, wherein R⁹ is selected from a groupconsisting of hydrogen, halogen, and alkyl; linear ether; cyclic ether.39. An article prepared from the polymer composition of claim
 1. 40. Thearticle of claim 39, wherein the article is a seal, a hose, a footwearinsole, a footwear midsole, a footwear outsole, an automotive bumper,sealing systems, hot melt adhesives, films, conveyor belts, sportivearticles, rotomolded articles, primers, linings, industrial flooring,and acoustic insulation.
 41. A method of preparing a polymercomposition, the method comprising: adding to a reactor ethylene, andone or more vinyl carbonyl monomers having the general structure:

 where R¹, R² and R³ are independently selected from a group consistingof hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,substituted alkoxy, alkenyl, substituted alkenyl, alkynyl, substitutedalkynyl, aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substitutedcycloalkyl, substituted cycloalkoxy, substituted aryl, and substitutedheterocycles; and Y and Z are independently selected from a groupconsisting of O, (CR^(5a)R^(5b)), (CHR_(6a))—R^(6b), phenylene, CH—OR⁷,and NR⁸, wherein R^(5a), R^(5b), R^(6a), R^(6b), and R⁸ areindependently selected from a group consisting of hydrogen, halogen,CH₂, and alkyl, and wherein R⁷ is independently selected from a groupconsisting of hydrogen; halogen; hydroxyl; alkyl; linear ether; cyclicether; Si(R⁹)₃, wherein R⁹ is independently selected from a groupconsisting of hydrogen, halogen, and alkyl; and (C═O)—R¹⁰, wherein R¹⁰is an alkyl; and R⁴ is independently selected from a group consisting ofhalogen, hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy,alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl,(heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substitutedcycloalkoxy, substituted aryl, and substituted heterocycles; andreacting the ethylene and one or more vinyl carbonyl monomers to producethe polymer composition with a number average molecular weight (M_(n))ranging from 5 kDa to 10000 kDa obtained by GPC.
 42. The method of anyclaim 41, wherein the one or more vinyl carbonyl monomers comprise vinylacetate and one or more comonomers.
 43. The method of claim 41, whereinthe method further comprises adding one or more diene comonomer to thereactor.
 44. The method of claim 41, wherein the reactor is ahigh-pressure reactor.
 45. The method of claim 41, wherein the pressureapplied in the reactor is 40 to 4,000 bar.
 46. The method of claim 41,wherein the temperature in the reactor during the reaction is 50° C. to350° C.